2h-1, 3, 5-oxadiazines



United States Patent O 3,310,554 2H-1,3,5-0XADIAZINES Robert A. Braun, Newark, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Mar. 31, 1965, Ser. No. 444,438 5 Claims. (Cl. 260-244) This application is acontinuation-in-part of application Ser. No. 289,416, filed June 20, 1963, now abandoned.

This invention relates to substituted oxadiazines and is more particularly directed to oxadiazines of the formula where R and R can be hydrogen; alkyl of 1 through 5 carbon atoms; alkyl of 1 through 5 carbon atoms substitutedwith such radicals as cyano, nitro, alkoxy of 1 through 5 carbon atoms, chlorine or fluorine; alkenyl of 2 through 5 carbon atoms; cycloalkyl of 4 through 7 carbon atoms; and phenyl; with the proviso that R and R can be joined together by an alkylene bridge of2through7carbon atoms; and X and Y can be perchloroalkyl, perfiuoroalkyl or mixed perchloro-perfluoroalkyl, all of 1 through 5 carbon atoms. By perchloroalkyl, perfiuor-oalkyl and perchlorofiuoroalkyl is meant such radicals as CF CF Cl, 3 7, 5 11, s, 2 5 4 9,

Preparation of the compounds These oxadiazines can be prepared by the reaction of a cyanamide with a perhaloket-one according to the following general equation:

where R, R X and Y are defined as in Formula 1.

The simple aliphatic cyanamides used in this reaction are available commercially. The more complicated substituted cyanamides can be made by the reaction of primary or secondary amines with cyanogen halides. Such a-reaction is described in more detail in U.S. Patents 2,985,683, 2,658,915, 2,443,504, and British Patent 549,368. are bridged can be prepared according to procedures disclosed in JACS, 72, 2280 (1949).

The lower perhaloketone reactants are also available commercially. The higher ketones can be made by methods described in detail in R. N. Hazeldine, J. Chem. Soc., 1748 (1 948) and M. Hauptschein and R. A. Braun, JACS, 77, 4930 (1955).

Those cyanamide reactants whose .R groups- The compounds of the invention are prepared according to Equation 2 by mixing suitable reactants, in stoichiometric proportions or with a slight excess of the cyanamide, and then either heating them in a bomb or refluxing them, the method depending on the boiling point of the ketone. The reaction can also be carried out in an inert solvent such as an aromatic or aliphatic hydrocarbon.

When conducted in a bomb, the reaction. is preferably run at a temperature of 25 to 175 C. In this temperature range, the reaction will take from 1 to 24 hours to complete, the actual time naturally depending on the temperature.

The product separates out as a solid, which can be removed from the reaction mass by such customary chemical procedures as filtration or centrifugation. This product can be either recrystallized from hydrocarbons, esters or ketones, or it can be purified by sublimation.

Utility 7 Because of the presence of amino groups in their structure, these oxadiazines can be used, in the usual concentrations, as catalysts for the polymerization of urethane polymers and epoxy resins.

Those compounds having ethylenically unsaturated substituents can be homopolyrnerized or can be used as cross-linking agents in other vinyl copolymers, using customary vinyl polymerization techniques. Such polymers, in turn, are useful in preparing coating compositions and textile finishes.

The compounds which contain free NH groups can be used as intermediates in the preparation of novel diisocyanates. Preparation of these diisocyanates can proceed according to the following equation:

B F; catalyst X X Y These diisocyanates can in turn be 'u-sedito insert fluorine atoms into polyureas and polyurethanes to enhance their water repellency and antisoiling properties.

Those compounds of the invention which are normally liquid at room temperature and-higher can also be used as heat transfer agents in hydraulic systems.

This invention will be better understood by referring to the following illustrative examples. In these examples, all parts are by weight.

EXAMPLE 1 amounts of any of the following substituted cyanamides and reacted with hexafluoroacetone in a similar fashion to give the corresponding listed oxadiazines of the invention:

bis(chlorodifluorornethyl)-2H-\1,3,5-oxadiazine, having a melting point of 160 C. was collected by filtration.

In a similar fashion, the following heterocyclic cyanamides can be reacted with hexafiuoroacetone, in the listed proportions to give the corresponding listed products:

The listed quantities of any of the following substituted cyanamides can be used in place of dimethyl cyanamide and reacted with dichlorotetrafluoroacetone to give'the corresponding listed oxadiazines of the invention:

Reaetant Amount Product N -w OHZCHZ H (LE 3 C 2 a CQCF:

' N (OIOH;;OH2)2NCN 167.0 (C1CHt-OI'I2)2N f I N(CHiOHgCl)z FsC CFa N NC-OHr-OHr-IYL-ON 171.0 NCCHzOH ITI-f -r;r oH,oH,oN

CeHs CaHa O N CeHs aC C a A P d t EXAMPLE 3 R t t t r 110 m an mom 0 A mixture of 41 parts of diallyl cyanarnide and 28.2 N parts of hexafluoroacetone was heated at 150 C. for four N-CN 48.0 N-f W- hours in a stainless steel bomb.

O N 55 The resulting 2,4-bis(diallylamino)-6,6=bis(trifiuoromethyl)-2H-1,3,5-oxidiazine was stripped at 0.1 millimeter ,49 of pressure to give a clear viscous liquid product.

N EXAMPLE 4 N-CN 55.0 N -N 0 To a solution of 4.2 parts of cyanamlde in about 17 O N ml. of ethyl ether were added dropwise, with stirring,

over one-half hour, 19.9 parts of dichlorotetrafluoro- Fae CFa acetone. JN The solution was allowed to 'cool to room temperature, N m and the crystalline solid which precipitated was removed 0 N by filtration and recrystallized from acetone to give 4,6- diamino 2,2 bis(dichlorofluoromethyl) 2H 1,3,5 F 6 CF; oxadiazine solvated with one-half mole of acetone, M.=P.

191 to 191.4 C. EXAMPLE 2 Seventy parts of dimethyl cyanamide were added to 199 parts of dichlorotetraflu-oroacetone. The mixture was then heated at C. for four hours under nitrogen and cooled.

A white crystalline solid, 2,4-bis(dimethylamino)-6,6-

The filtrate was evaporated at room temperature and reduced pressure, and the residual oil was heated to about C. for a few minutes. During this time, dichlorotetrafluoroacetone distilled off leaving behind crystalline 2,4 bis diamino 6,6 bis(dichlorofluoromethyl) 2H- 1,3,5-oxadiazine.

where R and R are selected from the group consisting of hydrogen; alkyl of 1 through 5 carbon atoms; alkyl of 1 through 5 carbon atoms substituted with a radical selected from the group consisting of cyano, nitro, alkoxy of 1 through 5 carbon atoms, chlorine and fluorine; alkenyl of 2 through 5 carbon atoms; cycloalkyl of 4 through 7 carbon atoms; and phenyl; with the proviso that R and R can be joined together by an alkylene bridge of 2 through 7 carbon atoms; and X and Y are selected from the group consisting of perchloroalkyl radicals, perfluoroalkyl radicals, and mixed perchloro-perfiuoroalkyl radicals, all of 1 through 5 carbon atoms.

2. 2,4 bis(dimethylamino) 6,6-bis(trifluoromethyl)- 2H-l,3,5-0Xadiazine.

3. 2,4 bis(dimethylamino) 6,6 bis(chlorodifiuoromethyl)-2H-1,'3,5-oxadiazine.

4. 2,4 bis(diallylamino) 6,6 bis(trifluoromethyD- 2'H-l,3,5-oxadiazine.

5. 2,4 bis diamino 6,6 bis(dichlorofluorbmethyD- 2H-1,3,5-oxadiazine.

No references cited.

WALTER A. MOiDANCE, Primary Examiner.

R. BOND, Assistant Examiner. 

1. A COMPOUND OF THE FORMULA 